CN101474896B - Ultra-hydrophobic film of compound structure - Google Patents

Abstract

The invention discloses a super-hydrophobic membrane with a composite structure, which comprises a membrane base, a bonding layer and a super-hydrophobic layer. Surface energy or/and micron-scale powder particles and nano-scale powder particles modified by low surface energy substances, and micron-scale protrusions and nano-scale protrusions are formed on the surface of the bonding layer. The superhydrophobic membrane of the present invention has a simple structure and is easy to manufacture , The cost is low, the water contact angle of the super-hydrophobic layer is 150°～165°, the rolling angle is less than 5°, the adhesive layer is set, there is no special requirement for the base material, and the super-hydrophobic structure can be set on the base with high hardness , the super-hydrophobic film itself can have certain strength and hardness, excellent mechanical properties, and can be used in occasions that require high mechanical properties, such as waterproof, anti-fouling, anti-fog, anti-snow, anti-icing, anti-oxidation, etc. Occasions: The film matrix is used, which occupies a small space and is convenient and simple to use.

Description

Composite Superhydrophobic Membrane

technical field

The invention relates to a super-hydrophobic structure, in particular to a super-hydrophobic film of a composite structure. the

Background technique

Surface wettability is an important property that determines the application of materials. Many physical and chemical processes, such as adsorption, lubrication, adhesion, dispersion, and friction, are closely related to surface wettability. Research on superhydrophobic surfaces has attracted great attention due to their potential applications in self-cleaning surfaces, microfluidic systems, and biocompatibility. The so-called super-hydrophobic surface generally refers to the rolling angle of water droplets with a contact angle of greater than 150° and less than 10°, which is waterproof, anti-icing, anti-fog, anti-snow, anti-fouling, dust-proof and prevents transmission lines from being caused by water droplets. Corona noise and other features. Therefore, it has broad application prospects in the fields of antifouling on building surfaces, radomes, chemical microreactors, and antifouling on transmission lines. the

In the prior art, there is a kind of utilizing plasma technology to use CF _Gas fluorinated polybutadiene membrane surface, generation and water contact angle are the superhydrophobic membrane of 157 °; Utilize photolithography to etch out a series of different Surfaces composed of different depths and columnar sections, and the surface is treated with hydrocarbons, siloxanes, and fluorocarbons to form a hydrophobic film on the surface; there is also a method of mixing aluminum acetylacetonate (AACA ) and titanium acetylacetonate compound (TACA), and then spread this mixture on a heat-resistant glass sheet at a speed of 1500rmp, and heat it at 500°C for 20s, so as to obtain a transparent biomimetic superhydrophobic nano- _TiO2 surface with self-cleaning function, etc. .

In the prior art, most of the methods for preparing superhydrophobic surfaces require the use of complex and expensive equipment and strict control of the preparation process. The cost of superhydrophobic structures is relatively high, and the large-scale application of superhydrophobic surfaces cannot be realized. At the same time, the preparation cost is relatively high, and the mechanical strength of the prepared superhydrophobic surface is not high, which cannot meet the actual needs. the

Therefore, there is a need for a superhydrophobic structure that is simple in structure, easy to manufacture, high in strength, low in cost, and can be manufactured and applied on a large scale. the

Contents of the invention

In view of this, the purpose of the present invention is to provide a superhydrophobic membrane with a composite structure. The superhydrophobic membrane has a simple structure, is easy to manufacture, has a high strength, is low in cost, and can be manufactured and applied on a large scale. The preparation method is simple Easy to operate and low production cost. the

The superhydrophobic membrane of the composite structure of the present invention comprises a membrane substrate, a bonding layer and a superhydrophobic layer, the bonding layer is bonded to the surface of the membrane substrate, and the superhydrophobic layer is composed of micron-sized powder particles arranged alternately and embedded in the bonding layer Composed of nano-scale powder particles, micro-scale powder particles and nano-scale powder particles form micro-scale protrusions and nano-scale protrusions on the surface of the bonding layer; the micro-scale powder particles and nano-scale powder particles have low surface energy or/and Modified by low surface energy substances, the distance between adjacent micron-scale protrusions is 500nm-100μm. the

Further, the particle size of the mixed powder of micron-sized powder and nano-sized powder is 60nm-100μm;

Further, the particle size of the mixed powder of micron-sized powder and nano-sized powder is 400nm-30μm;

Further, the micron-scale protrusion protrudes from the surface of 500nm-30μm, and the nano-scale protrusion protrudes from the surface of 20nm-1000nm;

Further, the protruding surface of the micron-scale protrusions is 500nm-15μm, the protruding surface of the nano-scale protrusions is 200nm-500nm, and the distance between adjacent micron-scale protrusions is 500nm-20μm;

Further, the bonding layer is one or more mixtures of vinyl fluoride-vinyl ether polymers, polyurethane resins, silicone resins and fluorine-containing acrylates;

Further, the micron-scale powder and nano-scale powder with low surface energy are one or more mixtures of polytetrafluoroethylene micropowder and perfluoroethylene propylene micropowder;

Further, the micron-scale powder and nano-scale powder modified by low surface energy substances are one or more mixtures of silicon dioxide, titanium dioxide, calcium carbonate and zinc oxide, which are used to modify the low surface energy The substance is one or more than one mixture of alkyl fluorosilane coupling agents with 8 to 19 carbon atoms or one or more than one of fluorine-containing acrylates with 6 to 18 fluorine atoms mixture;

Further, the material of the film base is one or a mixture of polyimide, polyester resin and polyarylene maple. the

Further, the material of the membrane base is one or a mixture of polyethylene, polypropylene, polyvinyl chloride and polytetrafluoroethylene. the

The beneficial effects of the present invention are: the superhydrophobic membrane of the composite structure of the present invention, the superhydrophobic layer is arranged in phases and embedded in the bonding layer on the surface of the film substrate and forms micron-scale protrusions and nano-scale protrusions of micron-scale powder particles and nano-scale Compared with other super-hydrophobic structures, the super-hydrophobic film of the present invention has high strength, simple structure, easy manufacture, and low cost. The water contact angle of the super-hydrophobic layer is 150°-165°, and the rolling angle is less than 5°. ; There is no special requirement for the base material when the adhesive layer is set up. The super-hydrophobic structure can be set on the base with high hardness. The super-hydrophobic film itself can have a certain strength and hardness, and has excellent mechanical properties. Occasions: The structure of embedded bonding is adopted, and the superhydrophobic layer is firmly combined with the film substrate through the adhesive layer, with stable performance and low cost, and can be used for waterproof, antifouling, antifog, antisnow, antiicing, antioxidation and other occasions; the use of the membrane matrix can make the use of the superhydrophobic membrane flexible, occupy a small space, be convenient and simple to use, easy to use, and easy to promote. It is a superhydrophobic structure that can be manufactured and applied on a large scale. the

Description of drawings

The present invention will be further described below in conjunction with the accompanying drawings and embodiments. the

Accompanying drawing is the structural representation of the present invention. the

Detailed ways

Accompanying drawing is the structural representation of the present invention, as shown in the figure:

Embodiment one

The superhydrophobic membrane of the composite structure of the present embodiment comprises a membrane substrate 1, an adhesive layer 4 and a superhydrophobic layer, the adhesive layer 4 is bonded to the membrane substrate 1, and the superhydrophobic layer is composed of micron-sized membranes arranged alternately and embedded in the adhesive layer. Composed of powder 2 and nano-scale powder 3, micron-scale powder 2 and nano-scale powder 3 form micron-scale protrusions and nano-scale protrusions on the surface of the bonding layer; in this embodiment, the material of the bonding layer is vinyl fluoride -Vinyl ether polymer, with good viscosity and strong adaptability, can be applied to various surfaces; micron-sized powder particles 2 and nano-sized powder particles 3 have low surface energy; in this embodiment, micron-sized powder particles with low surface energy Powder 2 and nanoscale powder 3 are polytetrafluoroethylene micropowders;

The particle size of the mixed powder of micron-scale powder 2 and nano-scale powder 3 is 60nm-100μm; The distance between them is 500nm-100μm. the

The superhydrophobic film prepared by using the micron-sized powder 2 and nano-sized powder 3 in this embodiment has stable performance, the water droplet contact angle is between 160°-162°, and the water droplet rolling angle is between 2°-4°. the

Example two

The superhydrophobic membrane of the composite structure of the present embodiment comprises a membrane substrate 1, an adhesive layer 4 and a superhydrophobic layer, the adhesive layer 4 is bonded to the membrane substrate 1, and the superhydrophobic layer is composed of micron-sized membranes arranged alternately and embedded in the adhesive layer. Composed of powder 2 and nanoscale powder 3, micron-scale powder 2 and nanoscale powder 3 form micron-scale protrusions and nano-scale protrusions on the surface of the bonding layer; in this embodiment, the material of the bonding layer is fluorine-containing Acrylic ester has stable physical properties and strong adaptability, and can be applied to various surfaces; micron-sized particles 2 and nano-sized particles 3 are modified with low surface energy substances. The micron-sized powder 2 and nano-sized powder 3 are silicon dioxide, of course, they can also be one or more mixtures of titanium dioxide, calcium carbonate and zinc oxide, all of which can achieve the purpose of the invention and are used for modified The low surface energy substance is heptadecafluorodecyltrimethoxysilane, of course, it can also be one or more mixtures of other alkyl fluorosilane coupling agents with 8 to 19 carbon atoms, or fluorine atoms One or more mixtures of fluorine-containing acrylates with a number of 6 to 18 can achieve the purpose of the invention;

The particle size of the mixed powder of micron-scale powder 2 and nano-scale powder 3 is 60nm-100μm; The distance between them is 500nm-100μm. the

The superhydrophobic film prepared by using the micron-sized powder 2 and nano-sized powder 3 of this embodiment has stable performance, the water droplet contact angle is between 154°-162°, and the water droplet rolling angle is between 2°-5°. the

Embodiment three

The superhydrophobic membrane of the composite structure of the present embodiment comprises a membrane substrate 1, an adhesive layer 4 and a superhydrophobic layer, the adhesive layer 4 is bonded to the membrane substrate 1, and the superhydrophobic layer is composed of micron-sized membranes arranged alternately and embedded in the adhesive layer. The powder 2 and the nano-scale powder 3 are composed, and the micro-scale powder 2 and the nano-scale powder 3 form micron-scale protrusions and nano-scale protrusions on the surface of the bonding layer; in this embodiment, the bonding layer material is polyurethane resin , stable physical properties, high viscosity, strong adaptability, applicable to various surfaces; micron-sized powder 2 and nano-sized powder 3 have low surface energy; in this embodiment, micron-sized powder 2 with low surface energy And nano-scale powder 3 is perfluoroethylene propylene micropowder;

The particle size of the mixed powder of micron-scale powder 2 and nano-scale powder 3 is 400nm-30μm; The distance between them is 500nm-20μm. the

The superhydrophobic film prepared by using the micron-sized powder 2 and nano-sized powder 3 in this embodiment has stable performance, the water droplet contact angle is between 162° and 167°, and the water droplet rolling angle is between 1° and 3°. the

Embodiment four

The superhydrophobic membrane of the composite structure of this embodiment comprises a membrane substrate 1, a bonding layer 4 and a superhydrophobic layer, the bonding layer 4 is bonded to the membrane substrate 1, and the superhydrophobic layer is composed of micron-sized powders arranged alternately and embedded in the bonding layer. granules 2 and nano-scale powder 3, micron-scale powder 2 and nano-scale powder 3 form micron-scale protrusions and nano-scale protrusions on the surface of the bonding layer; in this embodiment, the material of the bonding layer is silicone resin , stable physical properties, high viscosity, strong adaptability, and can be applied to various surfaces; micron-sized powder 2 and nano-sized powder 3 are modified by low surface energy substances. The modified micron-scale powder 2 and nano-scale powder 3 are calcium carbonate, and the low surface energy substance used for modification is dodecafluoroheptyl methacrylate;

The particle size of the mixed powder of micron-scale powder 2 and nano-scale powder 3 is 400nm-30μm; The distance between them is 500nm-20μm. the

The performance of the superhydrophobic film prepared by using the micron-sized powder 2 and the nano-sized powder 3 of this embodiment is stable, the contact angle of water droplets is between 160° and 165°, and the rolling angle of water droplets is between 1° and 4°. the

Of course, the binder is not limited to fluoroethylene-vinyl ether polymer, polyurethane resin, silicone resin, fluorine-containing acrylate, and can also be a mixture of more than one of the above substances, because its physical and chemical properties meet the requirements of the present invention. Cohesive requirements, thus can achieve the purpose of the invention;

The micron-sized powder 2 and nano-sized powder 3 with low surface energy described in Embodiment 1 and Embodiment 3 are not limited to polytetrafluoroethylene micropowder, but also perfluoroethylene propylene micropowder and a mixture of the two, All have the required properties of the present invention, can reach the purpose of the invention. the

In the above embodiments, the material of the film substrate is one or more mixtures of polyimide, polyester resin and polyarylene maple, which has soft physical properties, high strength and strong adaptability, and can be applied to various surfaces. , suitable for setting the adhesive layer, that is, the super-hydrophobic film is made into a tape structure, which is directly pasted during application, easy to use, and low in production cost;

The material of the membrane substrate can also be one or more mixtures of polyethylene, polypropylene, polyvinyl chloride and polytetrafluoroethylene, and the bonding effect of the adhesive layer is good, so that the superhydrophobic membrane can be applied to different Occasions, easy to use and flexible. the

During the preparation of the present invention, the micron-sized powder 2 and the nano-sized powder 3 are pressed into the upper surface of the adhesive layer on the surface of the substrate through a flat plate, and the surface of the cured adhesive layer is embedded with a super-hydrophobic surface layer. the

Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention without limitation. Although the present invention has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that the technical solutions of the present invention can be carried out Modifications or equivalent replacements without departing from the spirit and scope of the technical solution of the present invention shall be covered by the claims of the present invention. the

Claims (10)

1. a superhydrophobic membrane of composite structure, is characterized in that: comprise film substrate (1), adhesive layer (4) and superhydrophobic layer, described adhesive layer (4) is bonded in membrane substrate (1) surface , the superhydrophobic layer is composed of micron-sized powder particles (2) and nano-sized powder particles (1) arranged alternately and embedded in the bonding layer, and the micron-sized powder particles (2) and nano-sized powder particles (3) are in the bonding layer ( 4) micron-scale protrusions and nano-scale protrusions are formed on the surface; the micron-scale powder particles (2) and nano-scale powder particles (3) have low surface energy or/and are modified by low surface energy substances; adjacent micron-scale protrusions The spacing between them is 500nm-100μm. 2. The superhydrophobic membrane of composite structure according to claim 1, characterized in that: the particle size of the mixed powder of the micron-sized powder (2) and nano-sized powder (3) is 60nm-100μm. 3. The superhydrophobic membrane of composite structure according to claim 2, characterized in that: the particle size of the mixed powder of the micron-sized powder (2) and nano-sized powder (3) is 400nm-30μm. 4. The superhydrophobic film of composite structure according to claim 3, characterized in that: the micron-scale protrusions protrude from a surface of 500nm-30μm, and the nano-scale protrusions protrude from a surface of 20nm-1000nm. 5. The superhydrophobic film of the composite structure according to claim 4, characterized in that: the protruding surface of the micron-scale protrusions is 500nm-15 μm, the protruding surface of the nano-scale protrusions is 200nm-500nm, and the adjacent micron-scale protrusions The distance between them is 500nm-20μm. 6. The superhydrophobic membrane of the composite structure according to claim 5, characterized in that: the bonding layer is one of vinyl fluoride-vinyl ether polymer, polyurethane resin, silicone resin and fluorine-containing acrylate or a mixture of more than one. 7. the superhydrophobic membrane of composite structure according to claim 6 is characterized in that: micron-scale powder (2) and nano-scale powder (3) with low surface energy are polytetrafluoroethylene micropowder and perfluoroethylene One or more than one mixture of propylene micropowder. 8. the superhydrophobic film of composite structure according to claim 6, is characterized in that: described micron-scale powder (2) and nano-scale powder (3) that are modified by low surface energy substance are silicon dioxide, titanium dioxide A mixture of one or more of calcium carbonate and zinc oxide, the low surface energy substance used for modification is one or more of the alkyl fluorosilane coupling agents with 8 to 19 carbon atoms A mixture or a mixture of one or more fluorine-containing acrylates with 6-18 fluorine atoms. 9. The superhydrophobic membrane of the composite structure according to claim 7 or 8, characterized in that: the material of the membrane matrix (1) is one or one of polyimide, polyester resin and polyaryl maple a mixture of the above. 10. according to the superhydrophobic film of claim 7 or 8 described composite structures, it is characterized in that: the material of described film substrate (1) is a kind of in polyethylene, polypropylene, polyvinyl chloride and polytetrafluoroethylene or a mixture of more than one.